Carbon nanotubes buckypapers: A new frontier in wastewater treatment technology.

Occurrence of contaminants in water is one of the major global concerns humanity is still facing today: most of them are extremely toxic and dangerous for human health, obliging their removal for a proper and correct process of sanitation. Among wastewater treatment technologies, in the view of development of sustainable and environmentally friendly processes, membrane adsorption has proved to be a fast and simple method in the removal of pollutants, offering great contaminants recovery percentages, fast adsorbent regeneration and recycle, and easy scale-up. Due to their large surface area and tunable chemistry, carbon nanotubes (CNTs)-based materials revealed to be extraordinary adsorbents, exceeding by far performances of ordinary organic and inorganic membranes such as polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene, ceramics, currently employed in membrane technologies for wastewater treatment. In consideration of this, the review aims to summarize recent developments in the field of carbon nanotubes-based materials for pollutants recovery from water through adsorption processes. After a brief introduction concerning what adsorption phenomenon is and how it is performed and governed by using carbon nanotubes-based materials, the review discusses into detail the employment of three common typologies of CNTs-based materials (CNTs powders, CNTs-doped polymeric membranes and CNTs membranes) in adsorption process for the removal of water pollutants. Particularly focus will be devoted on the emergent category of self-standing CNTs membranes (buckypapers), made entirely of carbon nanotubes, exhibiting superior performances than CNTs and CNTs-doped polymeric membranes in terms of preparation strategy, recovery percentages of pollutants and regeneration possibilities. The extremely encouraging results presented in this review aim to support and pave the way to the introduction of alternative and more efficient pathways in wastewater treatment technologies to contrast the problem of water pollution.

Removal of Non-Steroidal Anti-Inflammatory Drugs from Drinking Water Sources by GO-SWCNT Buckypapers.

Pharmaceutical products such as antibiotics, analgesics, steroids, and non-steroidal anti-inflammatory drugs (NSAIDs) are new emerging pollutants, often present in wastewater, potentially able to contaminate drinking water resources. Adsorption is considered the cheapest and most effective technique for the removal of pollutants from water, and, recently, membranes obtained by wet filtration method of SWCNT aqueous solutions (SWCNT buckypapers, SWCNT BPs) have been proposed as self-standing porous adsorbents. In this paper, the ability of graphene oxide/single-walled carbon nanotube composite membranes (GO-SWCNT BPs) to remove some important NSAIDs, namely Diclofenac, Ketoprofen, and Naproxen, was investigated at different pH conditions (pH 4, 6, and 8), graphene oxide amount (0, 20, 40, 60, and 75 wt.%), and initial NSAIDs concentration (1, 10, and 50 ppm). For the same experimental conditions, the adsorption capacities were found to strongly depend on the graphene oxide content. The best results were obtained for 75 wt.% graphene oxide with an adsorption capacity of 118 ± 2 mg g-1 for Diclofenac, 116 ± 2 mg g-1 for Ketoprofen, and 126 ± 3 mg g-1 for Naproxen at pH 4. Overall, the reported data suggest that GO-SWCNT BPs can represent a promising tool for a cheap and fast removal of NSAIDs from drinking water resources, with easy recovery and reusability features.

A volume plasmon blueshift in thin silicon films embedded within Be/Si periodic multilayer mirrors.

Microstructural properties of the beryllium (Be) and silicon (Si) in periodic multilayer mirrors Be/Si with the variation of film thickness were comprehensively determined by Raman scattering. For the thinner films, the structure of Be evolved in the amorphous phase, and it was transformed into the polycrystalline phase for thicker films. The Si films in the periodic structure were condensed into the amorphous phase. The small fraction of nanocrystalline Si particles was distributed within the amorphous phase. A shake-up satellite peak of Si 2s photoelectrons was observed in X-ray photoelectron spectroscopy which suggested the excitation of a plasmon in Si films embedded within Be/Si periodic multilayers. The energy of plasmons was sensitive to the film thickness of Si in the periods which directly corresponds to the particle size. The binding energy of the satellite peak of Si 2s photoelectrons was blueshifted (higher energy) with a decrease in the particle size. This was explained by size dependent quantum confinement of particles.

Multivariate Metal-Organic Framework/Single-Walled Carbon Nanotube Buckypaper for Selective Lead Decontamination.

The search for efficient technologies empowering the selective capture of environmentally harmful heavy metals from wastewater treatment plants, at affordable prices, attracts wide interest but constitutes an important technological challenge. We report here an eco-friendly single-walled carbon nanotube buckypaper (SWCNT-BP) enriched with a multivariate amino acid-based metal-organic framework (MTV-MOF) for the efficient and selective removal of Pb2+ in multicomponent water systems. Pristine MTV-MOF was easily immobilized within the porous network of entangled SWCNTs, thus obtaining a stable self-standing adsorbing membrane filter (MTV-MOF/SWCNT-BP). SWCNT-BP alone shows a moderately good removal performance with a maximum adsorption capacity of 180 mg·g-1 and a considerable selectivity for Pb(II) ions in highly concentrated multi-ion solutions over a wide range of lead concentration (from 200 to 10000 ppb). Remarkably, these features were outperformed with the hybrid membrane filter MTV-MOF/SWCNT-BP, exhibiting enhanced selectivity and adsorption capacity (310 mg·g-1, which is up to 42% higher than that of the neat SWCNT-BP) and consequently enabling a more efficient and selective removal of Pb2+ from aqueous media. MTV-MOF/SWCNT-BP was able to reduce [Pb2+] from the dangerous 1000 ppb level to acceptable limits for drinking water, below 10 ppb, as established by the current EPA and WHO limits. Thus, the eco-friendly composite MTV-MOF/SWCNT-BP shows the potential to be effectively used several times as a reliable adsorbent for Pb2+ removal for household drinking water or in industrial treatment plants for water and wastewater lead decontamination.

Phase analysis of tungsten and phonon behavior of beryllium layers in W/Be periodic multilayers.

In periodic W/Be multilayers, thickness-dependent microstructural and phase modifications were investigated in W and Be layers. In X-ray diffraction, α-W was predominant for the ultrathin layer of W, while ß-W evolved along with the α-W phase for higher film thickness. For the thicker layers, the thermodynamically metastable ß-W vanished and a single well-defined preferably oriented stable α-W phase was observed. The lattice spacing revealed that these phases exist in the tensile stressed condition. With the increase in thickness of Be layers, the blueshift and narrow linewidth of the transverse optical (TO) phonon mode was observed in Raman scattering studies. However, the TO mode was redshifted and the linewidth was further narrowed consistently with an increase in the thermal annealing temperature of the multilayers. The investigation has quantified an increase in compressive strain and reduction of defects with an increase in thickness of the Be layers. However, for thermally annealed samples, the compressive strain in the Be layers was relaxed and crystalline quality was improved.

Phonon, plasmon and electronic properties of surfaces and interfaces of periodic W/Si and Si/W multilayers.

The phonon and plasmon excitations and electronic properties of interfaces of periodic W/Si and Si/W multilayer structures were investigated. The Boson band originated from quasilocal surface acoustic phonons for ultrathin Si layers, excited by Raman scattering. In confined Si layers, a small fraction of crystalline Si nanoclusters were embedded within a large volume fraction of amorphous Si (a-Si) nanoclusters. The size of the a-Si nanoclusters was smaller for the thinner Si layer in the periodic layers. The plasmon energy in the Si layer was blueshifted with a decrease in the thickness of this layer. This was explained by the size-dependent quantization of plasmon shift. The valence band spectra comprised a substantial fine structure, which is associated with the interaction of valence orbitals of the W and Si atoms at the interface boundaries. For thinner Si layers, the binding interaction of W5d and Si3p states leads to the splitting of the density of states near the Fermi level in the energy range of 1.5-5 eV. However, the energy splitting with two maxima was observed at 0.7 and 2.4 eV for thicker layers. Thus, the results of X-ray photoelectron spectroscopy have indicated that the interface of W/Si multilayers consists of metal-enriched tungsten silicide. Both the atomic structure and the elemental composition of the silicide were modified with a change in the thickness of the Si layers. This novel investigation could be essential for designing nanomirrors with higher reflectivity.

Optical Characterization of AsxTe100-x Films Grown by Plasma Deposition Based on the Advanced Optimizing Envelope Method.

Three AsxTe100-x films with different x and dissimilar average thickness are characterized mainly from one interference transmittance spectrum T(λ = 300 to 3000 nm) of such film on a substrate based on the advanced optimizing envelope method (AOEM). A simple dual transformation of T(λ) is proposed and used for increasing the accuracy of computation of its envelopes T+(λ) and T-(λ) accounting for the significant glass substrate absorption especially for λ > 2500 nm. The refractive index n(λ) of As40Te60 and As98Te2 films is determined with a relative error <0.30%. As far as we know, the As80Te20 film is the only one with anomalous dispersion and the thickest, with estimated = 1.1446 nm, ever characterized by an envelope method. It is also shown and explained why the extinction coefficient k(λ) of any of the three AsxTe100-x films is computed more accurately from the quantity Ti(λ) = [T+(λ)T-(λ)]0.5 compared to its commonly employed computation from T+(λ). The obtained results strengthen our conviction that the AOEM has a capacity for providing most accurate optical characterization of almost every dielectric or semiconductor film with > 300 nm on a substrate, compared to all the other methods for characterization of such films only from T(λ).

Infrared and Raman spectroscopy study of AsS chalcogenide films prepared by plasma-enhanced chemical vapor deposition.

AsS chalcogenide films, where As content is 60-40at.%, have been prepared via a RF non-equilibrium low-temperature argon plasma discharge, using volatile As and S as the precursors. Optical properties of the films were studied in UV-visible-NIR region in the range from 0.2 to 2.5µm. Infrared and Raman spectroscopy have been employed for the elucidation of the molecular structure of the newly developed material. It was established that PECVD films possess a higher degree of transparency (up to 80%) and a wider transparency window (>20µm) in comparison with the "usual" AsS thin films, prepared by different thermal methods, which is highly advantageous for certain applications.

Investigation of the composition-structure-property relationship of AsxTe100-x films prepared by plasma deposition.

AsxTe100-x amorphous films of different chemical content were prepared by Plasma-Enhanced Chemical Vapor Deposition (PECVD). For the first time the optical properties of As-Te chalcogenide materials have been measured in UV-VIS-IR ranges (from 0.2 to 25µm) for a very wide range of chemical compositions (20-80at.% As). As-Te films have been tuned from 0.80 to 1.10eV. The IR results obtained have been juxtaposed with the Raman spectroscopy findings to establish the correlation between optical and structural properties of the materials developed. Reversible and irreversible changes in the phase composition of the As-Te films under annealing of the surface by laser irradiation have been demonstrated and studied. In order to determine the potential areas of application of the prepared As-Te films the thermal and photo sensitivity has been also investigated.